Secondary Organic Aerosol Particles Research Articles

Fostering a Holistic Understanding of the Full Volatility Spectrum of Organic Compounds from Benzene Series Precursors through Mechanistic Modeling.

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NOx can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation.

Application of advanced causal analyses to identify processes governing secondary organic aerosols

Understanding how different physical and chemical atmospheric processes affect the formation of fine particles has been a persistent challenge. Inferring causal relations between the various measured features affecting the formation of secondary organic aerosol (SOA) particles is complicated since correlations between variables do not necessarily imply causality. Here, we apply a state-of-the-art information transfer measure coupled with the Koopman operator framework to infer causal relations between isoprene epoxydiol SOA (IEPOX-SOA) and different chemistry and meteorological variables derived from detailed regional model predictions over the Amazon rainforest. IEPOX-SOA represents one of the most complex SOA formation pathways and is formed by the interactions between natural biogenic isoprene emissions and anthropogenic emissions affecting sulfate, acidity and particle water. Since the regional model captures the known relations of IEPOX-SOA with different chemistry and meteorological features, their simulated time series implicitly include their causal relations. We show that our causal model successfully infers the known major causal relations between total particle phase 2-methyl tetrols (the dominant component of IEPOX-SOA over the Amazon) and input features. We provide the first proof of concept that the application of our causal model better identifies causal relations compared to correlation and random forest analyses performed over the same dataset. Our work has tremendous implications, as our methodology of causal discovery could be used to identify unknown processes and features affecting fine particles and atmospheric chemistry in the Earth’s atmosphere.

Technical note: Characterization of a single-beam gradient force aerosol optical tweezer for droplet trapping, phase transition monitoring, and morphology studies

Abstract. Single particle analysis is essential for a better understanding of the particle transformation process and to predict its environmental impact. In this study, we developed an aerosol optical tweezer (AOT) Raman spectroscopy system to investigate the phase state and morphology of suspended aerosol droplets in real time. The system comprises four modules: optical trapping, reaction, illumination and imaging, and detection. The optical trapping module utilizes a 532 nm laser and a 100 × oil immersion objective to stably trap aerosol droplets within 30 s. The reaction module allows us to adjust relative humidity (RH) and introduce reaction gases into the droplet levitation chamber, facilitating experiments to study liquid–liquid phase transitions. The illumination and imaging module employs a high-speed camera to monitor the trapped droplets, while the detector module records Raman scattering light. We trapped sodium chloride (NaCl) and 3-methyl glutaric acid (3-MGA) mixed droplets to examine RH-dependent morphology changes. Liquid–liquid phase separation (LLPS) occurred when RH was decreased. Additionally, we introduced ozone and limonene/pinene to generate secondary organic aerosol (SOA) particles in situ, which collided with the trapped droplet and dissolved in it. To determine the trapped droplet's characteristics, we utilized an open-source program based on Mie theory to retrieve diameter and refractive index from the observed whispering gallery modes (WGMs) in Raman spectra. It is found that mixed droplets formed core–shell morphology when RH was decreased, and the RH dependence of the droplets' phase transitions generated by different SOA precursors varied. Our AOT system serves as an essential experimental platform for in situ assessment of morphology and phase state during dynamic atmospheric processes.

Simulated phase state and viscosity of secondary organic aerosols over China

Abstract. Secondary organic aerosols (SOAs) can exist in liquid, semi-solid, or amorphous solid states. Chemical transport models (CTMs), however, usually assume that SOA particles are homogeneous and well-mixed liquids, with rapid establishment of gas–particle equilibrium for simulations of SOA formation and partitioning. Missing the information of SOA phase state and viscosity in CTMs impedes accurate representation of SOA formation and evolution, affecting the predictions of aerosol effects on air quality and climate. We have previously developed a parameterization to estimate the glass transition temperature (Tg) of an organic compound based on volatility and to predict viscosity of SOA. In this study, we apply this method to predict the phase state of SOA particles over China in summer of 2018 using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The simulated Tg of dry SOA (Tg,org) agrees well with the value estimated from ambient volatility measurements at an urban site in Beijing. For the spatial distributions of Tg,org, simulations show that at the surface the values of Tg,org range from ∼287 to 305 K, with higher values in northwestern China, where SOA particles have larger mass fractions of low-volatility compounds. Considering water uptake by SOA particles, the SOA viscosity shows a prominent geospatial gradient in which highly viscous or solid SOA particles are mainly predicted in northwestern China. The lowest and highest SOA viscosity values both occur over the Qinghai–Tibet Plateau, where the solid phase state is predicted over dry and high-altitude areas and the liquid phase state is predicted mainly in the south of the plateau with high relative humidity during the summer monsoon season. Sensitivity simulations show that, including the formation of extremely low-volatility organic compounds, the percent time that a SOA particle is in the liquid phase state decreases by up to 12 % in southeastern China during the simulated period. With an assumption that the organic and inorganic compounds are internally mixed in one phase, we show that the water absorbed by inorganic species can significantly lower the simulated viscosity over southeastern China. This indicates that constraining the uncertainties in simulated SOA volatility distributions and the mixing state of the organic and inorganic compounds would improve prediction of viscosity in multicomponent particles in southeastern China. We also calculate the characteristic mixing timescale of organic molecules in 200 m SOA particles to evaluate kinetic limitations in SOA partitioning. Calculations show that during the simulated period the percent time of the mixing timescale longer than 1 h is >70 % at the surface and at 500 hPa in most areas of northern China, indicating that kinetic partitioning considering the bulk diffusion in viscous particles may be required for more accurate prediction of SOA mass concentrations and size distributions over these areas.

Unpacking the diversity of monoterpene oxidation pathways via nitrooxy–alkyl radical ring-opening reactions and nitrooxy–alkoxyl radical bond scissions

Terrestrial vegetation emits vast quantities of monoterpenes to the atmosphere. These compounds, once oxidized, can contribute to the formation and growth of secondary organic aerosol (SOA) particles. However, studies report widely different SOA yields from atmospheric oxidation of different monoterpenes, despite their structural similarities. The NO3-radical-initiated oxidation of α-pinene for instance, leads to minimal SOA yields, whereas with Δ-carene a high SOA yield is observed. A previous study indicated that their oxidation mechanisms diverge after formation of a nitrooxy–alkoxyl radical intermediate, whose C–C bond scission reactions can either lead to early termination of the oxidative chain, thus limiting the yield of condensable vapors, or further propagate it, leading to low-volatility products. In this study, we employ computational methods to investigate these reactions in the NO3-radical oxidation of five other monoterpenes: limonene, sabinene, β-pinene, α-thujene and camphene. Additionally, we explore the possibility of rearrangement via ring-opening of the nitrooxy-alkyl radical adducts produced immediately after NO3 radical attack. Our calculations predict that alkyl radical rearrangement is dominant over O2-addition for sabinene, minor but competitive for α-thujene and β-pinene, and negligible for camphene. These rearrangements can induce further propagation of the oxidative chain, and thus higher SOA yields. Concerning alkoxyl radical C–C bond scissions, our results indicate that endocyclic nitrate species (derived from limonene and α-thujene) react preferentially via the channel leading to oxidative chain termination, whereas exocyclic nitrate species (sabinene, β-pinene, and camphene) react preferentially via channels leading to further propagation.

Characterization of the Vaporization Inlet for Aerosols (VIA) for online measurements of particulate highly oxygenated organic molecules (HOMs)

Abstract. Particulate matter has major climate and health impacts, and it is therefore of utmost importance to be able to measure the composition of these particles to gain insights into their sources and characteristics. Many methods, both offline and online, have been employed over the years to achieve this goal. One of the most recent developments is the Vaporization Inlet for Aerosols (VIA) coupled to a nitrate Chemical Ionization Mass Spectrometer (NO3-CIMS), but a thorough understanding of the VIA–NO3-CIMS system remains incomplete. In this work, we ran a series of tests to assess the impacts from different systems and sampling parameters on the detection efficiency of highly oxygenated organic molecules (HOMs) in the VIA–NO3-CIMS system. Firstly, we found that the current VIA system (which includes an activated carbon denuder and a vaporization tube) efficiently transmits particles (> 90 % for particles larger than 50 nm) while also removing gaseous compounds (> 97% for tested volatile organic compounds – VOCs). One of the main differences between the VIA and traditional thermal desorption (TD) techniques is the very short residence time in the heating region, on the order of 0.1 s. We found that this short residence time, and the corresponding short contact with heated surfaces, is likely one of the main reasons why relatively reactive or weakly bound peroxides, for example, were observable using the VIA. However, the VIA also requires much higher temperatures in order to fully evaporate the aerosol components. For example, the evaporation temperature of ammonium sulfate particles using the VIA was found to be about 100–150 °C higher than in typical TD systems. We also observed that the evaporation of particles with larger sizes occurred at slightly higher temperatures compared to smaller particles. Another major aspect that we investigated was the gas-phase wall losses of evaporated molecules. With a more optimized interface between the VIA and the NO3-CIMS, we were able to greatly decrease wall losses and thus improve the sensitivity compared to our earlier VIA work. This interface included a dedicated sheath flow unit to cool the heated sample and provide the NO3-CIMS with the needed high flow (10 L min−1). Our results indicate that most organic molecules observable by the NO3-CIMS can evaporate and be transported efficiently in the VIA system, but upon contact with the hot walls of the VIA, the molecules are instantaneously lost. This loss potentially leads to fragmentation products that are not observable by the NO3-CIMS. Thermograms, obtained by scanning the VIA temperature, were found to be very valuable for both quantification purposes and for estimating the volatility of the evaporating compounds. We developed a simple one-dimensional model to account for the evaporation of particles and the temperature-dependent wall losses of the evaporated molecules, and we thereby estimate the concentration of HOMs in secondary organic aerosol (SOA) particles. Overall, our results provide much-needed insights into the key processes underlying the VIA–NO3-CIMS method. Although there are still some limitations that could be addressed through hardware improvements, the VIA–NO3-CIMS system is a very promising and useful system for fast online measurements of HOMs in the particle phase.

Direct mitigation of secondary organic aerosol particulate pollutants by multiphase photocatalysis

Particulate matter represents one of the most severe air pollutants globally. Organic aerosol (OA) comprises 30–70 % of submicron particle mass in urban areas. An effective way to mitigate OA particulate pollutants is to reduce the formation of secondary organic aerosol (SOA). Here, we studied the effect of titanium dioxide (TiO2) photocatalytic seeds on the formation and mitigation of SOA particles from α-pinene or toluene oxidation in chamber. For the first time, we discovered that under ultraviolet (UV) irradiation, the presence of TiO2 directly removed internally mixed α-pinene SOA mass by 53.7 % within 200 mins, and also directly removed SOA matter in an externally mixed state that is not in direct contact with TiO2 surface: the mass of externally mixed α-pinene SOA was reduced by 21.9 % within 81 mins, and the toluene SOA mass was reduced by 46.6 % in 145mins. In addition, the presence of TiO2 effectively inhibited the formation of SOA particles with a SOA mass yield of zero. This study brings up an innovative concept for air pollution control - the direct photocatalytic degradation of OA with aid of TiO2-based photocatalysts. Our novel findings will potentially bring practical applications in air pollution abatement and regional, even global aerosol-climate interactions.

Effects of NO and SO2 on the secondary organic aerosol formation from isoprene photooxidation

Investigation of the effects of anthropogenic pollutants on the mass concentrations, particle number concentrations, and chemical compositions of secondary organic aerosol (SOA) formation is essential in understanding the photooxidation mechanism of volatile organic compounds but has been proven to be a very challenging experimental target because of their complex processes. Here, the effects of NO and SO2 on SOA formation from isoprene photooxidation were studied by a number of laboratory studies. The results indicate the accumulated O3 upon the NO conversion triggers the main oxidation reaction, by which the oxidants (i.e., OH and SO4−) are derived. The SOA mass concentrations and particle number concentrations are enhanced by NO under low NO concentrations but suppressed by NO under high NO concentrations, which are consistent with previous studies (Kroll et al., 2005, 2006). This could be rationalized that the large amount of accumulated O3 inhibit the multi-step isoprene oxidation and a large number of less oxidized products (m/z < 130) absorb or condense on the surface of existing particles, which decelerate the SOA nucleation and growth. The presence of SO2 accelerates the conversion of NO and the accumulation of O3, which promotes the main oxidation reaction of isoprene. New compounds are observed at m/z = 134, 137, 150, 152, and 179 measured by threshold photoionization (positive ion mode) with a tunable vacuum ultraviolet free electron laser and are found to be mainly formed from the isoprene oxidization by O3 and OH. The present findings provide both macroscopic and microscopic information to advance understanding of atmospheric components affected by the anthropogenic-biogenic interactions in the neighborhood of emission origins.

Indoor Air Quality Implications of Germicidal 222 nm Light.

One strategy for mitigating the indoor transmission of airborne pathogens, including the SARS-CoV-2 virus, is irradiation by germicidal UV light (GUV). A particularly promising approach is 222 nm light from KrCl excimer lamps (GUV222); this inactivates airborne pathogens and is thought to be relatively safe for human skin and eye exposure. However, the impact of GUV222 on the composition of indoor air has received little experimental study. Here, we conduct laboratory experiments in a 150 L Teflon chamber to examine the formation of secondary species by GUV222. We show that GUV222 generates ozone (O3) and hydroxyl radicals (OH), both of which can react with volatile organic compounds to form oxidized volatile organic compounds and secondary organic aerosol particles. Results are consistent with a box model based on the known photochemistry. We use this model to simulate GUV222 irradiation under more realistic indoor air scenarios and demonstrate that under some conditions, GUV222 irradiation can lead to levels of O3, OH, and secondary organic products that are substantially elevated relative to normal indoor conditions. The results suggest that GUV222 should be used at low intensities and in concert with ventilation, decreasing levels of airborne pathogens while mitigating the formation of air pollutants.

Phase State, Surface Tension, Water Activity, and Accommodation Coefficient of Water-Organic Clusters Near the Critical Size for Atmospheric New Particle Formation.

Interactions between water and organic molecules in sub-4 nm clusters play a significant role in the formation and growth of secondary organic aerosol (SOA) particles. However, a complete understanding of the relevant water microphysics has not yet been achieved due to challenges in the experimental characterization of soft nuclei. Here, we use molecular dynamics simulations to study the phase-mixing states, surface tension, water activity, and water accommodation coefficient of organic-water clusters representative of freshly nucleated SOA particles. Our results reveal large deviations from the behavior expected based on continuum theories. In particular, the phase-mixing state has a strong dependence on cluster size; surface tension displays a minimum at a specific organic-water mass ratio (morg/mw ∼ 4.5 in this study) corresponding to a minimum inhibition of droplet nucleation associated with the Kelvin effect; and the water accommodation coefficient increases by a factor of 2 with nanocluster hygroscopic growth, in agreement with recent experimental studies. Overall, our results yield parametric relations for water microphysical properties in sub-4 nm clusters and provide insight into the role of water in the initial stages of SOA nucleation and growth.

Viscosity, Glass Formation, and Mixing Times within Secondary Organic Aerosol from Biomass Burning Phenolics

Biomass burning events emit large amounts of phenolic compounds, which are oxidized in the atmosphere and form secondary organic aerosol (SOA). Using the poke-flow technique, we measured relative humidity (RH)-dependent viscosities of SOA generated by the oxidation of three biomass burning phenolic compounds: catechol, guaiacol, and syringol. All systems had viscosity < 3 × 103 Pa s at RH ≳ 40% and > 2 × 108 Pa s at RH ≲ 3% at room temperature. At RH values of 0–10%, the viscosities of these SOA were at least 2 orders of magnitude higher than the viscosity of primary organic aerosol from biomass burning. We also developed a parameterization for predicting the viscosity of phenolic biomass burning SOA as a function of RH and temperature. Based on this parameterization, the viscosity of phenolic biomass burning SOA is strongly dependent on both RH and temperature. Under dry conditions, phenolic biomass burning SOA is highly viscous at room temperature (∼109 Pa s) and becomes a glass (viscosity > 1012 Pa s) when the temperature is < 280 K. For tropospheric temperature and RH values, phenolic biomass burning SOA is often in a liquid state (η < 102 Pa s) below ∼2 km altitude, a semi-solid state (102 < η < 1012 Pa s) between ∼2 and ∼9 km, and a glassy state (η > 1012 Pa s) above ∼9 km. Furthermore, the mixing time of organic molecules in a 200 nm phenolic biomass burning SOA particle exceeds 1 h above 3 km in the troposphere.

Volatility of Secondary Organic Aerosol from β-Caryophyllene Ozonolysis over a Wide Tropospheric Temperature Range.

We investigated secondary organic aerosol (SOA) from β-caryophyllene oxidation generated over a wide tropospheric temperature range (213-313 K) from ozonolysis. Positive matrix factorization (PMF) was used to deconvolute the desorption data (thermograms) of SOA products detected by a chemical ionization mass spectrometer (FIGAERO-CIMS). A nonmonotonic dependence of particle volatility (saturation concentration at 298 K, C298K*) on formation temperature (213-313 K) was observed, primarily due to temperature-dependent formation pathways of β-caryophyllene oxidation products. The PMF analysis grouped detected ions into 11 compound groups (factors) with characteristic volatility. These compound groups act as indicators for the underlying SOA formation mechanisms. Their different temperature responses revealed that the relevant chemical pathways (e.g., autoxidation, oligomer formation, and isomer formation) had distinct optimal temperatures between 213 and 313 K, significantly beyond the effect of temperature-dependent partitioning. Furthermore, PMF-resolved volatility groups were compared with volatility basis set (VBS) distributions based on different vapor pressure estimation methods. The variation of the volatilities predicted by different methods is affected by highly oxygenated molecules, isomers, and thermal decomposition of oligomers with long carbon chains. This work distinguishes multiple isomers and identifies compound groups of varying volatilities, providing new insights into the temperature-dependent formation mechanisms of β-caryophyllene-derived SOA particles.

Glass Transition Temperatures of Organic Mixtures from Isoprene Epoxydiol-Derived Secondary Organic Aerosol.

The phase states and glass transition temperatures (Tg) of secondary organic aerosol (SOA) particles are important to resolve for understanding the formation, growth, and fate of SOA as well as their cloud formation properties. Currently, there is a limited understanding of how Tg changes with the composition of organic and inorganic components of atmospheric aerosol. Using broadband dielectric spectroscopy, we measured the Tg of organic mixtures containing isoprene epoxydiol (IEPOX)-derived SOA components, including 2-methyltetrols (2-MT), 2-methyltetrol-sulfate (2-MTS), and 3-methyltetrol-sulfate (3-MTS). The results demonstrate that the Tg of mixtures depends on their composition. The Kwei equation, a modified Gordon-Taylor equation with an added quadratic term and a fitting parameter representing strong intermolecular interactions, provides a good fit for the Tg-composition relationship of complex mixtures. By combining Raman spectroscopy with geometry optimization simulations obtained using density functional theory, we demonstrate that the non-linear deviation of Tg as a function of composition may be caused by changes in the extent of hydrogen bonding in the mixture.

Insect Infestation Increases Viscosity of Biogenic Secondary Organic Aerosol.

Plant stress alters emissions of volatile organic compounds. However, little is known about how this could influence climate-relevant properties of secondary organic aerosol (SOA), particularly from complex mixtures such as real plant emissions. In this study, the chemical composition and viscosity were examined for SOA generated from real healthy and aphid-stressed Canary Island pine (Pinus canariensis) trees, which are commonly used for landscaping in Southern California. Healthy Canary Island pine (HCIP) and stressed Canary Island pine (SCIP) aerosols were generated in a 5 m3 environmental chamber at 35-84% relative humidity and room temperature via OH-initiated oxidation. Viscosities of the collected particles were measured using an offline poke-flow method, after conditioning the particles in a humidified air flow. SCIP particles were consistently more viscous than HCIP particles. The largest differences in particle viscosity were observed in particles conditioned at 50% relative humidity where the viscosity of SCIP particles was an order of magnitude larger than that of HCIP particles. The increased viscosity for the aphid-stressed pine tree SOA was attributed to the increased fraction of sesquiterpenes in the emission profile. The real pine SOA particles, both healthy and aphid-stressed, were more viscous than α-pinene SOA particles, demonstrating the limitation of using a single monoterpene as a model compound to predict the physicochemical properties of real biogenic SOA. However, synthetic mixtures composed of only a few major compounds present in emissions (<10 compounds) can reproduce the viscosities of SOA observed from the more complex real plant emissions.

Light absorption and scattering properties of indole secondary organic aerosol prepared under various oxidant and relative humidity conditions

Secondary organic aerosol (SOA) from indole was produced in a smog chamber under different relative humidity (RH = <2%, 25% and 50%) and with different oxidants (O3, OH, OH + NOx, and NO3). The mass absorption coefficients were measured by extracting SOA in methanol and taking absorption spectra in the 200-700 nm range. Chromophoric compounds were tentatively identified by liquid chromatography – spectrophotometry – mass spectrometry. One of the strongest chromophores was nitroindole, produced in high abundance by both NO3 and OH + NOx oxidation. Indole SOA was also prepared in an oxidation flow reactor (OFR) using the same set of oxidants under variable RH conditions. Densities of the OFR-generated SOA particles ranged from 1.05 g/cm3 for indole + O3 SOA to 1.33 g/cm3 for indole + OH SOA. The real (n) and imaginary (k) refractive indices were quantified using a broadband cavity-enhanced spectrometer (BBCES) over the 360–425 nm spectral range. The values of k ranged from 10−2 to 10−1 at 405 nm, which is comparable to those for humic-like substances and at least an order of magnitude larger than k values of SOA produced from other biogenic and anthropogenic volatile organic compounds. The k values for the indole + NO3 SOA had a strong and non-monotonic dependence on RH, suggesting two competing reaction mechanisms for the chromophores, highlighting the complex effect of water on the absorption coefficient of SOA from heterocyclic aromatic precursors. Strong absorption of indole SOA may contribute to the degradation of visibility near its emission sources, which include animal husbandry facilities and stressed plants.Copyright © 2023 American Association for Aerosol Research

The impacts of air quality and secondary organic aerosols formation on traffic accidents in heavy fog–haze weather

This study estimated changes in the levels of three components of regional haze, namely fine particulate matter (PM2.5), relative humidity (RH), and secondary organic aerosols (SOAs), at the time of two severe traffic accidents on a coastal expressway and a freeway in the Jianan Plain in southwestern Taiwan to understand the impact of weather and air quality factors on the low visibility. Monitoring data and surveillance images from four nearby air quality monitoring stations were collected to determine the precise causes of the poor visibility–related accidents. The study applied a haze extraction method to the images to achieve demisting, and the processed data were used to assess the relationship between the haze components and visibility during the accidents. The correlation between visibility and the haze components was assessed. The results revealed that the RH levels dropped significantly at the time of the accidents, signifying that moisture was not the main haze–fog component. The haze components can be ordered as follows in terms of their correlation with (and thus effect on) local visibility: PM2.5 > SOAs > RH. The spatial distributions and evolutions of the three components indicated that the PM2.5 concentrations remained high from midnight until early morning but decreased slightly at the time of both accidents. By contrast, the concentration of ultrafine SOA particles, which can scatter and absorb light to reduce road visibility, increased rapidly before both accidents. Therefore, PM2.5 and SOAs were two non-negligible factors of low visibility during the accidents, especially SOAs.

Isothermal evaporation of α-pinene secondary organic aerosol particles formed under low NOx and high NOx conditions

Abstract. Many recent secondary organic aerosol (SOA) studies mainly focus on biogenic SOA particles formed under low NOx conditions and thus are applicable to pristine environments with minor anthropogenic influence. Although interactions between biogenic volatile organic compounds and NOx are important in, for instance, suburban areas, there is still a lack of knowledge about the volatility and processes controlling the evaporation of biogenic SOA particles formed in the presence of high concentrations of NOx. Here we provide detailed insights into the isothermal evaporation of α-pinene SOA particles that were formed under low NOx and high NOx conditions to investigate the evaporation process and the evolution of particle composition during the evaporation in more detail. We coupled Filter Inlet for Gases and AEROsols-Chemical Ionization Mass Spectrometer (FIGAERO-CIMS) measurements of the molecular composition and volatility of the particle phase with isothermal evaporation experiments conducted under a range of relative humidity (RH) conditions from low RH (&lt;7 % RH) to high RH (80 % RH). Very similar changes were observed in particle volatility at any set RH during isothermal evaporation for the α-pinene SOA particles formed under low NOx and high NOx conditions. However, there were distinct differences in the initial composition of the two SOA types, possibly due to the influence of NOx on the RO2 chemistry during SOA formation. Such compositional differences consequently impacted the primary type of aqueous-phase processes in each type of SOA particle in the presence of particulate water.

Kinetics of oligomer-forming reactions involving the major functional groups present in atmospheric secondary organic aerosol particles.

Atmospheric organic aerosol particles impact climate as well as human and environmental health. Secondary organic aerosol (SOA), which is formed by the gas-to-particle partitioning of products of the oxidation of volatile organic compounds (VOCs) emitted from biogenic or anthropogenic sources, contributes a large fraction of this material. In the particle phase, these products can undergo accretion reactions to form oligomers that impact the formation, composition, and chemical-physical properties of aerosols. While these reactions are known to occur in the atmosphere, data and models describing their kinetics and equilibria are sparse. Here, reactions of compounds containing potentially reactive hydroperoxide, hydroxyl, carboxyl, aldehyde, and ketone groups were investigated in single and phase-separated organic/aqueous mixtures in the absence and presence of a sulfuric acid catalyst. Compounds containing these groups and a nonreactive UV-absorbing nitrate group were synthesized and their reactions and products were monitored and characterized using high-performance liquid chromatography with UV detection (HPLC-UV), electrospray ionization-mass spectrometry (ESI-MS), and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Reactions were observed between hydroperoxides and aldehydes to form peroxyhemiacetals, and between carboxylic acids and alcohols to form esters, and their rate and equilibrium constants were determined. No reactions were observed in other mixtures, indicating that under the conditions of these experiments only a few reaction pathways form oligomers. Reactions were also conducted with probe compounds and SOA formed in an environmental chamber reaction of α-pinene with O3. Whereas in a previous study we observed a rapid hydroperoxide reaction in this SOA, among the other compounds studied here only alcohols reacted. These results provide insight into the types of accretion reactions that are likely to occur in atmospheric aerosols, and the rate and equilibrium constants can be used to better model SOA chemistry.

Effects of NO2 and SO2 on the secondary organic aerosol formation from [formula omitted]-pinene photooxidation

Elucidating the effects of anthropogenic pollutants on the photooxidation of biogenic volatile organic compounds is crucial to understanding the fundamental mechanisms of secondary organic aerosol (SOA) formation. Here, the impacts of NO2 and SO2 on SOA formation from the photooxidation of a representative monoterpene, β-pinene, were investigated by a number of laboratory studies. The results indicated NO2 enhanced the SOA mass concentrations and particle number concentrations under both low and high β-pinene conditions. This could be rationalized that the increased O3 concentrations upon the NOx photolysis was helpful for the generation of more amounts of O3-oxidized products, which accelerated the SOA nucleation and growth. Combing with NO2, the promotion of the SOA yield by SO2 was mainly reflected in the increase of mass concentration, which might be due to the elimination of the newly formed particles by the initially formed particles. The observed low oxidation degree of SOA might be attributed to the fast growth of SOA, resulting in the uptake of less oxygenated gas-phase species onto the particle phase. The present findings have important implications for SOA formation affected by anthropogenic–biogenic interactions in the ambient atmosphere.

Sunlight can convert atmospheric aerosols into a glassy solid state and modify their environmental impacts

Secondary organic aerosol (SOA) plays a critical, yet uncertain, role in air quality and climate. Once formed, SOA is transported throughout the atmosphere and is exposed to solar UV light. Information on the viscosity of SOA, and how it may change with solar UV exposure, is needed to accurately predict air quality and climate. However, the effect of solar UV radiation on the viscosity of SOA and the associated implications for air quality and climate predictions is largely unknown. Here, we report the viscosity of SOA after exposure to UV radiation, equivalent to a UV exposure of 6 to 14 d at midlatitudes in summer. Surprisingly, UV-aging led to as much as five orders of magnitude increase in viscosity compared to unirradiated SOA. This increase in viscosity can be rationalized in part by an increase in molecular mass and oxidation of organic molecules constituting the SOA material, as determined by high-resolution mass spectrometry. We demonstrate that UV-aging can lead to an increased abundance of aerosols in the atmosphere in a glassy solid state. Therefore, UV-aging could represent an unrecognized source of nuclei for ice clouds in the atmosphere, with important implications for Earth's energy budget. We also show that UV-aging increases the mixing times within SOA particles by up to five orders of magnitude throughout the troposphere with important implications for predicting the growth, evaporation, and size distribution of SOA, and hence, air pollution and climate.